US5462847A - Silver halide color photographic material - Google Patents
Silver halide color photographic material Download PDFInfo
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- US5462847A US5462847A US08/070,294 US7029493A US5462847A US 5462847 A US5462847 A US 5462847A US 7029493 A US7029493 A US 7029493A US 5462847 A US5462847 A US 5462847A
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- silver halide
- photographic material
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- heterocyclic
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/381—Heterocyclic compounds
- G03C7/382—Heterocyclic compounds with two heterocyclic rings
- G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
- G03C1/14—Methine and polymethine dyes with an odd number of CH groups
- G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
- G03C1/22—Methine and polymethine dyes with an even number of CH groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
Definitions
- the present invention relates to a silver halide color photographic material. More particularly, the present invention relates to a silver halide color photographic material which has an excellent capability of being rapidly processed, exhibits a small sensitivity change with the fluctuations of the temperature upon exposure (dependence on the exposure temperature) and a small change in sensitivity and gradation with time after the preparation of coating solution.
- photographic light-sensitive materials comprising a silver halide emulsion are utilized for various purposes in the market.
- the market scale has recently grown.
- photographic light-sensitive materials for color print requires an enhancement of the development speed which directly leads to an enhancement of print productivity.
- JP-A As used herein means an "unexamined published Japanese patent application”
- JP-A-2-42 discloses that the use of a sensitizing dye having a specified reduction potential improves the dependence of a high silver chloride content emulsion on the exposure temperature.
- the use of such a sensitizing dye causes a change in sensitivity and gradation with time after the preparation of a coating solution and before the coating thereof, and further improvements are needed to supply color photographic papers with stable properties to photofinishing laboratories.
- the present market has a strong demand for color photographic light-sensitive materials which can be rapidly processed and stably finished. It is therefore an object of the present invention to provide a silver halide color photographic material which has an excellent capability of being rapidly processed, exhibits a small change due to the fluctuations of the temperature upon exposure (dependence on the exposure temperature) and a small change in sensitivity and gradation with time after the preparation of coating solutions.
- a silver halide color photographic material comprising at least one yellow-developable silver halide emulsion layer, at least one magenta-developable silver halide emulsion layer and at least one cyan-developable silver halide emulsion layer on a support, characterized in that said at least one cyan-developable silver halide emulsion layer comprises at least one cyan dye-forming coupler represented by the following general formula (Ia) and silver bromochloride or silver chloride emulsion grains substantially free of silver iodide having a silver chloride content of 95 mol % or more, spectrally sensitized with at least one sensitizing dye having a reduction potential of -1.27 V (vs.
- Za represents --NH-- or --CH(R 3 ); Zb and Zc each represents --C(R 4 ) ⁇ or --N ⁇ ; R 1 , R 2 and R 3 each represents an electron withdrawing group having a Hammett's substituent constant ⁇ p value of 0.20 or more, with the proviso that the sum of ⁇ p of R 1 and R 2 is 0.65 or more; R 4 represents a hydrogen atom or substituent, with the proviso that if two R 4 's are present in the general formula, they may be the same or different; X represents a hydrogen atom or a split-off group from the rest of the structure upon coupling reaction with an oxidation product of an aromatic primary amine color developing agent; and R 1 , R 2 , R 3 , R 4 or X may be a divalent group which is connected to a dimer or higher polymer or a high molecular chain to form a homopolymer or copolymer.
- the at least one sensitizing dye to be used in the cyan-developable silver halide emulsion layer is selected from the group consisting of red-sensitive sensitizing dyes represented by the general formulae (A), (B), (C) and (D): ##STR3## wherein Z 1 , Z 2 , Z 4 and Z 5 each represents a sulfur atom or selenium atom; Z 6 and Z 7 each represents an oxygen atom, sulfur atom, selenium atom or R--N in which R has the same meaning as R' 19 defined below, with the proviso that at least one of Z 6 and Z 7 represents an oxygen atom or R--N; Z 8 represents an oxygen atom, sulfur atom, selenium atom or R'--N in which R' has the same meaning as R' 19 ; Z 9 represents an oxygen atom, sulfur atom or R'--N in which R" has the same meaning as R' 19 ; Z 3 represents an atomic group necessary for the formation of a 5- or 6-membered ring
- R' 17 and L 8 , and/or R' 18 and L 9 may be connected to each other to form a 5- or 6-membered carbon ring;
- R' 19 represents an alkyl group, aryl group or heterocyclic group;
- R' 15 represents an alkyl group or alkoxy group;
- V 20 , V 21 , V 22 , V 23 , V 24 , V 25 , V 26 , V 27 and V 28 each represents a hydrogen atom, halogen atom, alkyl group, acyl group, acyloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxyl group, cyano group,
- cyan coupler of the present invention represented by the general formula (Ia) include those represented by the following general formulae (IIa) to (VIIIa): ##STR4## wherein R 1 , R 2 , R 3 , R 4 and X are as defined in the general formula (Ia).
- cyan couplers Preferred among these cyan couplers are those represented by the general formulae (IIa), (IIIa) and (IVa), particularly (IIIa).
- R 1 , R 2 and R 3 each is an electron withdrawing group having a Hammett's substituent constant ⁇ p of 0.20 or more, with the proviso that the sum of ⁇ p of R 1 and R 2 is 0.65 or more, preferably 0.70 or more and not more than 1.8.
- R 1 , R 2 and R 3 each is an electron withdrawing group having a Hammett's substituent constant ⁇ p of 0.20 or more, preferably 0.35 or more, more preferably 0.60 or more, and not more than 1.0.
- Hammett's rule is an empirical law which was proposed in 1935 by L. P. Hammtt to give a quantative discussion of the effect of substituents on the reaction or equilibrium of benzene derivatives. This rule is now widely considered reasonable.
- Substituent constants determined by Hammett's rule include ⁇ p value and ⁇ m value which can be found in many general references, e.g., J. A. Dean, "Lange's Handbook of Chemistry", vol.
- R 1 , R 2 and R 3 are defined by Hammett's substituent constant ⁇ p . However, this does not mean that these substituents are limited to those having known ⁇ p values found in the above cited references. It goes without saying that even these substituents exhibit ⁇ p values unknown in any reference, they are included in those having ⁇ p values that would be included in the range known in these references when measured according to Hammett's rule.
- R 1 , R 2 and R 3 having a ⁇ p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted by other electron withdrawing groups having a ⁇ p value of 0.20 or more, hetero
- the electron withdrawing group having a ⁇ p value of 0.20 or more include acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), acyloxy group (e.g., acetoxy), carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-(4-n-pentadecanamide)phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-[3-(2,4-di-t-amylphenoxy)-propyl ⁇ carbamoyl), alkoxycarbonyl group (e.g., acetyl,
- Typical examples of ⁇ p value of electron withdrawing group include 0.66 for cyano group, 0.78 for nitro group, 0.54 for trifluoromethyl group, 0.50 for acetyl group, 0.92 for trifluoromethanesulfonyl group, 0.72 for methanesulfonyl group, 0.70 for benzenesulfonyl group, 0.49 for methanesulfinyl group, 0.36 for carbamoyl group, 0.45 for methoxycarbonyl group, 0.37 for pyrazolyl group, 0.36 for methanesulfonyloxy group, 0.60 for dimethoxyphosphoryl group, and 0.57 for sulfamoyl group.
- R 1 , R 2 and R 3 include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group, halogenated aryloxy group, halogenated aryl group, and aryl group substituted by two or more nitro groups and heterocyclic group substituted by two or more nitro groups.
- acyl group alkoxycarbonyl group, aryloxycarbonyl group, nitro group, cyano group, arylsulfonyl group, carbamoyl group, and halogenated alkyl group. More preferred among these groups are cyano group, alkoxycarbonyl group, aryloxycarbonyl group, and halogenated alkyl group.
- R 1 and R 2 are preferably that R 1 is a cyano group and R 2 is any of a trifluoromethyl group, a straight-chain or branched unsubstituted alkoxycarbonyl group, an alkoxycarbonyl group substituted with a carbamoyl group, an alkoxycarbonyl group having an ether bond, and an aryloxycarbonyl group that is either unsubstituted or substituted with an alkyl group or an alkoxy group.
- R 4 represents a hydrogen atom or substituent (including atom).
- substituents include halogen atom, aliphatic group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkenyloxy group, formyl group, alkylacyl group, arylacyl group, heterocyclic acyl group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl
- R 4 include hydrogen atom, halogen atom (e.g., chlorine, bromine), aliphatic group (e.g., C 1-36 straight-chain or branched alkyl group, aralkyl group, alkenyl group, alkinyl group, cycloalkyl group, cycloalkenyl group, such as methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3- ⁇ 4- ⁇ 2-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido ⁇ phenyl ⁇ propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-t-amylphenoxy)propyl), aryl group (e.g., C 6-36 aryl group, such
- R 4 Preferred among these groups represented by R 4 are alkyl group, aryl group, heterocyclic group, cyano group, nitro group, acylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, imido group, sulfinyl group, phosphonyl group, acyl group, and azolyl group.
- alkyl group and aryl group.
- Further preferred among these groups are alkyl group or aryl group containing at least one alkoxy, sulfonyl, sulfamoyl, carbamoyl, acylamido or sulfonamido group as a substituent.
- Particularly preferred among these groups are alkyl group or aryl group containing at least one acylamido or sulfonamido group as a substituent.
- X represents a hydrogen atom or a group which is separated from the rest of the molecule when the coupler reacts with an oxidation product of an aromatic primary amine color developing agent (hereinafter referred to as "split-off group").
- the split-off group represented by X is a halogen atom; aromatic azo group; alkyl, aryl, heterocyclic, alkylsulfonyl, arylsulfonyl, arylsulfinyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic oxycarbonyl, alkylcarbonyl, arylcarbonyl, heterocyclic carbonyl, alkylaminocarbonyl, arylaminocarbonyl or heterocyclic aminocarbonyl group connected to the coupling position via oxygen, nitrogen, sulfur or carbon atom; or heterocyclic group connected to the coupling position via a nitrogen atom contained therein.
- split-off groups include halogen atom, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, alkylsulfonamide group, arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylthio group, arylthio group, heterocyclic thio group, carbamoylamino group, arylsulfinyl group, arylsulfonyl group, 5- or 6-membered nitrogen-containing heterocyclic group, imido group, and arylazo group.
- the alkyl group, aryl group or heterocyclic group may be further substituted by substituents described with reference to R 4 .
- substituents described with reference to R 4 When two or more of such substituents are present, they may be the same or different.
- These substituents may be further substituted by substituents described with reference to R 4 .
- split-off groups include halogen atom (e.g., fluorine, chlorine, bromine), alkoxy group (e.g., ethoxy, dodecyloxy, methoxyethyl carbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy group (e.g., 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), alkylsulfonyloxy group or arylsulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), acylamino group (e.
- split-off group connected to the rest of the molecule via a carbon atom via a carbon atom there may be used a bis-type coupler obtained by condensing a four-equivalent coupler with aldehyde or ketone.
- the split-off group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.
- Preferred examples of the group represented by X include halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, arylsulfonyl group, arylsulfinyl group, and 5- or 6-membered nitrogen-containing heterocyclic group connected to the coupling active position via a nitrogen atom.
- Preferred among these groups is arylthio group.
- R 1 , R 2 , R 3 , R 4 or X may contain a cyan coupler residue represented by the general formula (Ia) to form a dimer or higher polymer, or R 1 , R 2 , R 3 , R 4 or X may contain a high molecular chain to form a homopolymer or copolymer.
- a typical example of the homopolymer or copolymer containing a high molecular chain is a homopolymer or copolymer of addition polymer ethylenically unsaturated compounds containing a cyan coupler residue represented by the general formula (Ia).
- Such a polymer may contain one or more kinds of cyan-coloring repeating units containing a cyan coupler residue represented by the general formula (Ia).
- Such a polymer may also be a copolymer containing one or more kinds of noncoloring ethylenic monomers which don't undergo coupling with an oxidation product of an aromatic primary amine developing agent such as acrylic ester, methacrylic ester and maleic ester.
- the compound of the present invention and intermediates thereof can be synthesized by known methods. For example, methods described in J. Am. Chem. Soc., No. 80, 5332 (1958), J.A,. Chem. Soc., No. 81, 2452 (1959), J.A,. Chem. Soc., No. 112, 2465 (1990), Org. Synth., I, 270 (1941), J. Chem. Soc., 5149 (1962), Heterocycles, No. 27, 2301 (1988), Rec. Tray. chim., 80, 1075 (1961), articles cited therein, or analogous methods can be used.
- the melting point of the compound was 97° C. to 98° C.
- the cyan coupler of the present invention represented by the general formula (Ia) is applied to a silver halide color photographic material, at least one layer containing the coupler of the present invention may be present on a support.
- the layer containing the coupler of the present invention may be a hydrophilic colloidal layer on the support.
- at least one blue-sensitive silver halide emulsion layer, one blue-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer may be coated on a support in this order or different orders.
- an infrared-sensitive silver halide emulsion layer may be used instead of at least one of these light-sensitive emulsion layers.
- These light-sensitive emulsion layers can each comprise a silver halide emulsion sensitive to the respective wavelength range and a color coupler which forms a dye complementary to the light to which the silver halide emulsion is sensitive to provide color reproduction in subtractive color process.
- the light-sensitive emulsion layer and the color hue of color coupler may not have the aforementioned correspondence.
- the coupler of the present invention represented by the general formula (Ia) is applied to a photographic light-sensitive material, it is particularly preferably incorporated in a red-sensitive silver halide emulsion layer.
- the amount of the coupler of the present invention to be incorporated in the photographic light-sensitive material is in the range of 1 ⁇ 10 -3 mol to 1 mol, preferably 2 ⁇ 10 -3 mol to 5 ⁇ 10 -1 mol per mol of silver halide.
- the sensitizing dye to be incorporated in the cyan-developable silver halide emulsion layer of the present invention preferably exhibits a reduction potential of -1.29 V (vs SCE) or lower.
- the measurement of reduction potential was carried out by phase discrimination secondary harmonics alternating polarography. The measurement process will be further described below.
- As a solvent for sensitizing dye there was used acetonitrile (spectral grade) dried in 4A-1/16 Molecular Sieves (trade name, available from Wako Junyaku K.K.) with a normal tetrapropyl ammonium perchloroate (special reagent for polarography) as a supporting electrolyte.
- Vycor glass was used for the liquid connecting portion. The measurement was carried out at a temperature of 25° C. with the tip of the rugin tube and the tip of mercury capillary being 5 mm to 8 mm apart. The measurement of reduction potential by phase discrimination secondary harmonics alternating voltammetry using platinum as a work electrode is described in "Journal of Imaging Science", vol. 30, pp. 27-35, 1986.
- R' 11 , R' 12 , R' 13 , R' 14 , R' 16 , R' 17 and R' 18 in these general formulae include unsubstituted alkyl groups containing 18 or less carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), and substituted alkyl groups containing 18 or less carbon atoms ⁇ examples of such substituents include carboxy groups, sulfo groups, cyano groups, halogen atom (e.g., fluorine, chlorine, bromine), hydroxyl groups, alkoxycarbonyl groups containing 8 or less carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy groups containing 8 or less carbon atoms (e.g.,
- sulfamoyl groups e.g., sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl
- aryl groups containing 10 or less carbon atoms e.g., phenyl, 4-chlorophenyl, 4-methylphenyl, ⁇ -naph
- R' 16 and L 4 , and/or R' 17 and L 8 , and/or R' 18 and L 9 may be connected to each other to form a 5- or 6-membered carbon ring.
- R' 19 is preferably C 1-18 , more preferably C 1-7 , particularly C 1-4 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl group ⁇ e.g., aralkyl (e.g., benzyl, 2-phenylethyl), hydroxylalkyl (e.g., 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl (e.g., 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl (e.g., 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl), sulfoalkyl (e.g., 2-sulfoethyl, 3-
- R' 15 include C 1-3 unsubstituted alkyl groups (e.g., methyl, ethyl, propyl), C 1-4 substituted alkyl groups ⁇ e.g., alkyl substituted by substituents such as C 1-2 alkoxy groups (e.g., methoxy, ethoxy) ⁇ , and C 1-3 alkoxy groups (e.g., methoxy, ethoxy).
- C 1-3 unsubstituted alkyl groups e.g., methyl, ethyl, propyl
- C 1-4 substituted alkyl groups ⁇ e.g., alkyl substituted by substituents such as C 1-2 alkoxy groups (e.g., methoxy, ethoxy) ⁇
- C 1-3 alkoxy groups e.g., methoxy, ethoxy
- Preferred among these groups are methyl groups, ethyl groups, and methoxy groups. Particularly preferred among these groups are methyl groups.
- Z 3 is preferably a 5- or 6-membered carbon ring, and more preferably 2,2-dimethyl-trimethylene.
- Z 1 , Z 2 , Z 4 and Z 5 each represents a sulfur atom or selenium atom, preferably sulfur atom.
- Z 6 and Z 7 each represents an oxygen atom, sulfur atom, selenium atom or R--N in which R has the same meaning as R' 19 , with the proviso that at least one of Z 6 and Z 7 represents an oxygen atom or nitrogen atom.
- Z 6 and Z 7 each represents a sulfur atom or oxygen atom, and at least one of them represents an oxygen atom.
- Z 8 represents an oxygen atom, sulfur atom, selenium atom or R'--N in which R' has the same meaning as R' 19 , preferably sulfur atom.
- Z 9 represents an oxygen atom, sulfur atom, selenium atom or R"--N in which R" has the same meaning as R' 19 , preferably sulfur atom.
- V 17 to V 28 which are connected to adjacent carbon atoms may be connected to each other to form a condensed ring.
- a condensed ring examples include benzene ring and heterocycle (e.g., pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole).
- Y 1 is more preferably -0.30 or less, and Y 2 is more preferably -0.45 or less.
- ⁇ p represents a value set forth in "Yakubutsu no Kozokassei Sokan-Drug Design to Sayokisaku Kenkyu eno Shishin(Relationship between structure and activity of chemicals)" ("Kagaku no Ryoiki(Region of Chemistry)", No. 122, Kozo Kassei Sokan Konwakaihen), pp. 96-103, Nankodo, and Corwin Hansh and Albert Leo, "Substituent Constants for Correlation Analysis in Chemistry and Biology", pp. 69-161, John Wiley and Sons. The method for the measurement of ⁇ p is described in “Chemical Reviews", vol. 17, pp. 125-136, 1935.
- V 1 to V 16 include hydrogen atoms, unsubstituted alkyl groups having 6 or less carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), substituted alkyl groups having 8 or less carbon atoms (e.g., carboxymethyl, 2-carboxyethyl, benzyl, phenethyl, dimethylaminopropyl), hydroxyl groups, amino groups (e.g., amino, hydroxylamino, methylamino, dimethylamino, diphenylamino), alkoxy groups (e.g., methoxy, ethoxy, isopropoxy, propoxy, butoxy, pentoxy), aryloxy groups (e.g., phenoxy), and ary
- L 4 , L 5 , L 6 , L 7 , L 8 , L 9 , L 10 , L 11 and L 12 each represents a methine group which may be substituted by a substituted or unsubstituted alkyl group (e.g., methyl, ethyl), substituted or unsubstituted aryl group (e.g., phenyl) or a halogen atom or may form a ring with other methine groups.
- a substituted or unsubstituted alkyl group e.g., methyl, ethyl
- substituted or unsubstituted aryl group e.g., phenyl
- a halogen atom e.g., a halogen atom
- r 1 , r 2 , r 3 and r 4 each may have a proper value of 0 or more as necessary. Whether a dye is a cation or anion or has a net ionic charge or not depends on its auxochrome and substituents. A typical cation is an inoganic or organic ammonium ion or alkaline ion.
- a typical anion may be either an inorganic anion or organic anion.
- examples of such an anion include halogen anion (e.g., fluoride ion, chloride ion, bromide ion, iodide ion), substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g., 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, pictate
- sensitizing dye to be used in the present invention represented by the general formulae (A), (B), (C) and (D) will be given below, but the present invention should not be construed as being limited thereto.
- Exemplary Compounds (A-1) to (A-17) set forth in Table A indicate specific examples of substituents in the general formula (A) (Z 1 and Z 2 each represents S, Z 3 represents 2, 2-dimethyltrimethylene group, V 1 , V 4 , V 5 , V 8 each represents hydrogen atom).
- the addition of the compound represented by the general formula (A), (B), (C) or (D) to be used in the present invention to a silver halide emulsion can be accomplished by any method well known in the art.
- the compound of the present invention may be added to the silver halide emulsion in solution in one or an admixture of water-soluble solvents such as methanol, ethanol, pyridyl, methyl cellosolve and acetone or a mixture of such an organic solvent with water.
- the compound of the present invention may be added to the silver halide emulsion at any time during the preparation thereof, preferably during the chemical ripening of the emulsion, or either before or after the addition of a stabilizer or fog inhibitor after the completion of the chemical ripening.
- the added amount of the compound (A), (B), (C) or (D) to be used in the present invention is not specifically limited but is normally in the range of 1 ⁇ 10 -6 to 1 ⁇ 10 -3 mol, preferably 1 ⁇ 10 -5 to 5 ⁇ 10 -4 mol per mol of silver halide.
- a sensitizing dye having a spectral sensitivity particularly to a wavelength range from red to infrared a compound described in JP-A-2-157749, lower right column, page 13 to lower right column, page 22 may be added.
- the use of such a compound can specifically enhance the preservability, processing stability and super-sensitizability of the photographic light-sensitive material.
- the combined use of compounds represented by the general formulae (IV), (V) and (VI) disclosed in the above cited publication is preferable.
- Such a compound is used in an amount of 0.5 ⁇ 10 -5 mol to 5.0 ⁇ 10 -2 mol, preferably 5.0 ⁇ 10 -5 mol to 1.0 ⁇ 10 -2 mol per mol of silver halide.
- the advantageous amount of such a compound to be used is from 1 to 10,000 times, preferably 2 to 5,000 times per mol of sensitizing dye.
- a yellow-developable silver halide emulsion layer, a magenta-developable silver halide emulsion layer, and a cyan-developable silver halide emulsion layer are coated on a support in this order.
- These light-sensitive emulsion layers can each comprise a silver halide emulsion sensitive to the respective wavelength range and a so-called color coupler which forms a dye complementary to the light to which it is sensitive (i.e., yellow for blue, magenta for green, cyan for red) to provide color reproduction in a substractive color process.
- the light-sensitive layer and the color hue of the coupler may not have the aforementioned correspondence.
- silver halide emulsion to be used in the present invention there may be preferably used an emulsion comprising silver chloride, silver bromochloride or silver bromochloroiodide having a silver chloride content of 95 mol % or more, preferably having a silver iodide content of 1 mol % or less, more preferably 0.2 mol % or less.
- the halogen composition of emulsion may be the same or different from grain to grain.
- the use of an emulsion having the same halogen composition among grains advantageously provides easy uniformalization of the properties of grains.
- the halogen composition distribution in the silver halide emulsion grain can be properly selected from the group consisting of so-called uniform-type structures in which the halogen composition is the same anywhere, so-called laminated structures in which the halogen composition differs from the core to the shell [single or plural], and structures in which nonlayer portions having different halogen compositions are localized inside or on the grains (portions having different halogen compositions are fused to the edge, corner or surface of the grains).
- the border of the portions having different compositions may be a definite one or an indefinite one where a mixed crystal is formed by the difference in the halogen composition or a positively continuous structural change.
- Such a high silver chloride emulsion may preferably have a silver bromide-rich phase localized inside and/or on silver halide grains in a layer or non-layer form as mentioned above.
- the halogen composition of the aforementioned localized phase preferably has a silver bromide content of at least 10 mol %, more preferably 20 mol % or more.
- These localized phases may be preferably present inside the grains, on the edge or corner of the surface of the grains, or on the surface of the grains, particularly on the corner of the grains.
- uniform structure grains having a small inner halogen composition distribution may be preferably used.
- the average grain size (number-average value of grain sizes as calculated in terms of diameter of circle having the same area as that of projected area of grains) of silver halide grains contained in the silver halide emulsion to be used in the present invention is preferably in the range of 0.1 ⁇ m to 2 ⁇ m.
- the silver halide grains to be contained in the photographic emulsion may have a regular crystal form such as cube, octahedron and tetradecahedron, an irregular crystal form such as sphere and tablet or composite thereof.
- the silver halide grains also may comprise a mixture of grains having various crystal forms.
- grains having the aforementioned regular crystal forms are contained in a weight proportion of 50% or more, preferably 70% or more, more preferably 90% or more.
- the preparation of emulsion to be used in the present invention can be accomplished by any suitable method as disclosed in P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967, G. F. Duffin, "Photographic Emulsion Chemistry", The Focal Press, 1966, and V. L. Zelikman et al., “Making and Coating Photographic Emulsion", The Focal Press, 1964.
- the emulsion can be prepared by any of the acid process, the neutral process, the ammonia process, etc.
- the reaction between a soluble silver salt and a soluble halogen salt can be carried out by any of a single jet process, a double jet process, a combination thereof, and the like.
- the silver halide emulsion to be used in the present invention may be subjected to chemical sensitization and spectral sensitization.
- the chemical sensitization can be accomplished by sulfur sensitization exemplified by the addition of an unstable sulfur compound, selenium sensitization, noble metal sensitization exemplified by gold sensitization, or reduction sensitization, singly or in combination.
- the gelatin to be used in the present invention there may be preferably used deionized gelatin.
- most gelatins contain calcium ions as much as 5,000 ppm or more.
- the deionized gelatin to be used in the present invention there may be preferably used those containing calcium ions in an amount of 500 ppm or less.
- the deionized gelatin may be preferably used in an amount of 10% by weight or more, more preferably 20% by weight or more, particularly 50% by weight or more based on the total weight of gelatins. Such a gelatin may be incorporated in any layers.
- the cyan coupler-containing layer and magenta coupler-containing layer, or yellow coupler-containing layer and interlayer of the present invention may comprise an inhibitor for color mixing incorporated therein.
- ultraviolet absorbent to be incorporated in the upper portion of the cyan coupler-containing layer of the present invention there may be used any proper compound.
- Preferred examples of such an ultraviolet absorbent include thiazolidone, benzotriazole, acrylonitrile, benzophenone and aminobutadiene ultraviolet absorbents. Examples of these ultraviolet absorbents are disclosed in U.S. Pat. Nos. 1,023,859, 2,685,512, 2,739,888, 2,784,087, 2,748,021, 3,004,896, 3,052,636, 3,215,530, 3,253,921, 3,533,794, 3,692,525, 3,705,805, 3,707,375, 3,738,837, and 3,754,919, and British Patent 1,321,355.
- magenta coupler there may be preferably used 5-pyrazolone magenta coupler or pyrazoloazole magenta coupler.
- imidazol[1,2-b]pyrazoles as disclosed in U.S. Pat. No. 4,500,630 are preferred in the light of the reduction of yellow secondary absorption and the light fastness of imaging dye.
- pyrazol[1,5-b]-[1,2,4]triazole disclosed in U.S. Pat. No. 4,540,654 is preferred.
- pyrazolotriazole couplers having branched alkyl group directly connected to the 2, 3 or 6-position of pyrazoloazole ring as described in JP-A-61-65245 pyrazoloazole couplers containing sulfonamide group in molecule as described in JP-A-61-65246, pyrazoloazole couplers having alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and pyrazoloazole couplers having alkoxy group or aryloxy group in the 6-position as described in European Patent Disclosure No. 226,849 and 294,785 may be preferably used.
- the photographic additives such as cyan, magenta and yellow couplers to be used in the present invention may be preferably used in solution in a high boiling organic solvent.
- a high boiling organic solvent there may be used any good solvent for coupler nonmiscible with water having a melting point of 100° C. or lower and a boiling point of 140° C. or higher.
- the melting point of such a high boiling organic solvent is preferably 80° C. or lower.
- the boiling point of such a high boiling organic solvent is preferably 160° C. or higher, more preferably 170° C. or higher.
- the cyan, magenta or yellow coupler may be infiltrated through a loadable latex polymer (as disclosed in U.S. Pat. No. 4,203,716) in the presence or absence of the aforementioned high boiling organic solvent or dissolved with a water-insoluble and organic solvent-soluble polymer, and then emulsion-dispersed in an aqueous solution of a hydrophilic colloid.
- a loadable latex polymer as disclosed in U.S. Pat. No. 4,203,716
- Homopolymers or copolymers as described in U.S. Pat. No. 4,857,449, 7th column to 15th column, and WO88/00723, pp. 12-30, may be preferably used. More preferably, methacrylate or acrylamide polymers, particularly acrylamide polymers may be used.
- the light-sensitive material of the present invention may preferably comprise a dye image preservability improving compound as disclosed in European Patent 0,277,589A2 in combination with couplers, particularly pyrazoloazole couplers or pyrroloazole cyan couplers of the present invention.
- a compound (F) which undergoes chemical bonding to an aromatic amine developing agent remaining after color development to produce a chemically inert and substantially colorless compound and/or a compound (G) which undergoes chemical bonding to an oxidation product of an aromatic amine color developing agent remaining after color development to produce a chemically inert and substantially colorless compound may be preferably used singly or in combination to inhibit the occurrence of stain or other side effects caused by the formation of developed dyes by the reaction of a color developing agent or its oxidation product remaining in the film with a coupler in the storage after processing.
- the light-sensitive material of the present invention may preferably comprise an antifungal substance as disclosed in JP-A-63-271247 to prevent from various mold and bacteria which can be propagated in the hydrophilic colloidal layer to deteriorate the image.
- the support to be used in the light-sensitive material of the present invention there can be used a white polyester support for display or a support having a white pigment-containing layer on a basic support of the silver halide emulsion layer side.
- an antihalation layer may be preferably coated on the silver halide emulsion side or opposite side of the support.
- the transmission density of the support is preferably adjusted to a range of 0.35 to 0.8.
- a support there may be used a reflective support or transmission support. More preferably, a reflective support may be used for the objects of the present invention.
- the light-sensitive material of the present invention may be exposed to visible light or infrared light. Exposure may be carried out by a low intensity exposure process or a high intensity short time exposure process. In the latter case, laser scanning exposure process with an exposure time of less than 10 -4 seconds per pixel may be preferably used.
- a band stop filter as disclosed in U.S. Pat. No. 4,880,726 may be preferably used for exposure. This removes light stain, providing a remarkable enhancement of color reproducibility.
- a method for the processing of a silver halide color photographic material comprising a high silver chloride emulsion having a silver chloride content of 90 mol % or more there may be preferably used a method described in JP-A-2-207250, upper left column, page 27 to upper right column, page 34.
- Emulsion R 1 thus obtained was then evaluated for the grain shape, grain size and grain size distribution from its electron microphotograph.
- the emulsion grains were cubic.
- the grain size was 0.58 ⁇ m.
- the grain size fluctuation coefficient was 0.09.
- the grain size is represented by the average of diamter of circles having the same area as the projected area of grains.
- the grain size fluctuation coefficient is obtained by dividing the standard deviation of grain sizes by the average grain size.
- Emulsion R 2 was prepared in the same manner as Emulsion R 1 except that the temperatue at which the aqueous solution of silver nitrate and the aqueous solution of sodium chloride were mixed was altered.
- the grain size and fluctuation coefficient of Emulsion R 2 thus obtained were 0.45 ⁇ m and 0.11, respectively.
- a polyethylene double-laminated paper support was subjected to corona discharge on its surface.
- a gelatin undercoating layer containing sodium dodecylbenzenesulfonate was coated on the surface of the support.
- Various photographic constituent layers were further coated on the undercoating layer to prepare a multi-layer color photographic paper having the following layer configuration (Specimen 101).
- the coating solution used had been prepared as follows:
- a cyan coupler (Exemplary Compound 11), 10.4 g of an ultraviolet absorbent (UV-2), 19.1 g of a dye image stabilizer (Cpd-1), 0.58 g of a dye image stabilizer (Cpd-9), 8.7 g of a dye image stabilizer (Cpd-10), 8.7 g of a dye image stabilizer (Cpd-11), 0.58 g of a dye image stabilizer (Cpd-8), and 0.58 g of a dye image stabilizer (Cpd-12) were added 30.8 cc of ethyl acetate, 12.7 g of a solvent (Solv-6) and 0.58 g of a solvent (Solv-1) to make a solution.
- UV-2 ultraviolet absorbent
- Cpd-1 dye image stabilizer
- Cpd-9 0.58 g of a dye image stabilizer
- Cpd-10 8.7 g of a dye image stabilizer
- Cpd-11 8.7 g of a dye image stabilizer
- the solution was then added to 265 cc of a 20% aqueous solution of gelatin containing 37 cc of 10% sodium dodecylbenzenesulfonate.
- the material was then subjected to emulsion dispersion by an ultrasonic homogenizer to prepare an emulsion dispersion C.
- the emulsion dispersion C and the silver bromochloride emulsion R were mixed to prepare a 5th layer coating solution having the following composition.
- a red-sensitive sensitizing dye Exemplary Compound 17
- an aminostilbene compound were added to the material to effect spectral sensitization.
- Silver halide emulsions and coating solutions for other layers were prepared in the same manner as the 5th layer.
- Cpd-15 and Cpd-16 were each added to these layers in a total amount of 25.0 mg/m 2 and 50.0 mg/m 2 , respectively.
- the silver bromochloride emulsion in these light-sensitive emulsion layers comprised the following spectral sensitizing dyes:
- Green-sensitive Emulsion Layer (4.0 ⁇ 10 -4 mol per mol of silver halide for the large size emulsion and 5.6 ⁇ 10 -4 mol per mol of silver halide for the small size emulsion) (7.0 ⁇ 10 -5 mol per mol of silver halide for the large size emulsion and 1.0 ⁇ 10 -4 mol per mol of silver halide for the small size emulsion)
- Red-sensitive Emulsion Layer (0.9 ⁇ 10 -4 mol per mol of silver halide for the large size emulsion and 1.1 ⁇ 10 -4 mol per mol of silver halide for the small size emulsion)
- green-sensitive emulsion layer and red-sensitive emulsion layer was each added 1-(5-methylureidophenyl)-5-mercaptotetrazole in an amount of 3.4 ⁇ 10 -5 mol, 9.7 ⁇ 10 -4 mol and 5.5 ⁇ 10 -4 mol per mol of silver halide, respectively.
- the silver halide emulsions used in the various silver halide emulsion layers were prepared in the same manner as Emulsion R 1 .
- the formulations of the various layers are set forth below.
- the figures indicate the coated amount (g/m 2 ).
- the coated amount of silver halide emulsion is represented as calculated in terms of silver.
- Polyethylene-laminated paper [containing a white pigment (TiO 2 ) and a bluish dye (ultramarine) in polyethylene on the 1st layer side]
- UV-1 Ultraviolet Absorbent
- UV-2 Ultraviolet Absorbent
- Specimens 102 to 121 were prepared in the same manner as Specimen 101 except that the cyan coupler and red-sensitive sensitizing dye to be incorporated in the 5th layer were replaced by cyan couplers and sensitizing dyes selected from exemplary compounds of the present invention or comparative couplers, etc. which are shown in Table B.
- coating was conducted 30 minutes after the preparation of the 5th layer coating solution.
- Specimens 401 to 421 were prepared in the same manner as Specimens 101 to 121 except that the time between the preparation of the 5th layer coating solution and the coating of the coating compositions was altered to 4 hours.
- these specimens were stored at temperatures of 15° C. and 35° C. (55% RH) for 30 minutes, and then subjected to gradationwise exposure for sensitometry through blue, green and red filters by means of a sensitometer (FWH, avaialbe from Fuji Photo Film Co., Ltd.; color temperature of light source: 3,200° K) at the respective temperatures.
- the exposure was conducted in such a manner that an exposure of 250 CMS was reached in 0.1 second.
- Specimen 101 which had been exposed to light was continuously processed with the following processing solutions in the following processing procedures by means of a paper processing machine in such a manner that a running balance state was obtained. The other specimens were then processed.
- Ion-exchanged water (calcium and magnesium concentration: 3 ppm or less each)
- the difference in the logarithm of the exposure (sensitivity) required to obtain a density of 1.0 between 15° C. exposure and 35° C. exposure was determined. The nearer to zero this difference is, the more improved is the dependence on exposure temperature.
- the sensitivity change with ageing time of the coating solution the sensitivity of specimens which had been exposed at a temperature of 15° C. was compared between Specimens 101 to 121 and Specimens 401 to 421. The nearer to zero this difference is, the less is the sensitivity change with ageing time of the coating solution.
- Specimens 102 to 107 which comprise cyan couplers not according to the present invention, showed an appreciable difference in the dependence on exposure temperature and the sensitivity change with ageing time of the coating solution from one sensitizing dye to another.
- Specimens 102 and 107 comprise sensitizing dyes of the present invention to improve the dependence on exposure temperature but exhibit an increased desensitization with ageing time of the coating solution.
- Specimen 101, Specimens 108 to 110, and Specimens 114 to 121 which comprise sensitizing dyes and cyan couplers of the present invention, exhibit an improved dependence on exposure temperature and a reduced desensitization with ageing time of the coating solution.
- Silver halide emulsions R 3 and R 4 were prepared in the same manner as the silver halide emulsions R 1 and R 2 to be used in the 5th layer coating solution of Example 1 except that chloroauric acid was used in addition to the sulfur sensitizer (triethylthiourea) for the optimum chemical sensitization.
- Emulsions G 3 , G 4 , B 3 and B 4 were prepared in the same manner as Emulsions G 1 , G 2 , B 1 and B 2 except that the chemical sensitization was similarly changed.
- Specimens 201, 203, and 207 to 211 which comprise coating solution aged 30 minutes
- Specimens 501, 503, and 507 to 511 which comprise coating solution aged 4 hours, as set forth in Table D
- Table D Specimens 101, 103, 107 to 111, 401, 403, and 407 to 411 except that the silver halide emulsions R 1 , R 2 , B 1 , B 2 , G 1 and G 2 were replaced by silver halide emulsions R 3 , R 4 , B 3 , B 4 , G 3 and G 4 , respectively, and the yellow couplers to be incorporated in the 1st layer were replaced by E ⁇ 3Y, respectively, in the equimolecular amount.
- These specimens were evaluated in the same manner as in Example 1. ##
- Table E shows that the effects of the present invention become more remarkable when a gold-sensitized emulsion is used.
- Specimens were prepared in the same manner as Specimen 101 of Example 1 except that the layer constitution and yellow couplers used were altered as set forth below. Further specimens were prepared in the same manner as all the specimens used in Examples 1 and 2 except that the layer constitution and yellow couplers used were similarly altered. These specimens were examined in the same manner as in Example 1. Also in the present example, mercaptotetrazoles, tetrazaindenes, gelatin hardeners, irradiation-inhibiting dyes, and spectral sensitizing dyes as used in Example 1 were used.
- the formulations of the various layers are set forth below.
- the figures indicate the coated amount (g/m 2 ).
- the coated amount of silver halide emulsion is represented as calculated in terms of silver.
- Polyethylene-laminated paper [containing a white pigment (TiO 2 ) and a bluish dye (ultramarine) in polyethylene on the 1st layer side]
- UV-3 UV-3
- Specimens 501 to 540 were prepared in the same manner as in Example 1 except that the sensitizing dye and cyan coupler to be incorporated in the 5th layer were altered as set forth in Table F. These specimens were evaluated in the same manner as in Example 1. For the evaluation of the ageing stability of the coating solution, specimens were prepared in the same manner as Specimens 501 to 540 except that the coating solutions were aged for different times as in Example 1.
- Example 2 Combined with the results of Example 1, the aforementioned results show that only the combination according to the present invention can provide an excellent dependence on exposure temperature and a reduced desensitization due to the ageing of the coating solution.
- the present invention provides a silver halide color photographic material which has an excellent capability of being rapidly processed, exhibits a small sensitivity change with the fluctuations of the temperature upon exposure (dependence on the exposure temperature) and a small change in sensitivity and gradation with ageing time of the coating solution.
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Abstract
Description
(1) ##STR5## (2) ##STR6## (3) ##STR7## (4) ##STR8## (5) ##STR9## (6) ##STR10## (7) ##STR11## ##STR12## No. R.sub. 1 R.sub.2 R.sub.4 X 8 CO.sub.2 CH.sub.3 CN ##STR13## H 9 CN ##STR14## ##STR15## H 10 CN ##STR16## ##STR17## H 11 CN ##STR18## ##STR19## H 12 CN ##STR20## ##STR21## H 13 CN ##STR22## ##STR23## H 14 CN CO.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2).sub.6 F ##STR24## H 15 CN ##STR25## ##STR26## ##STR27## 16 CN CO.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2).sub.6 F ##STR28## ##STR29## 17 CN ##STR30## ##STR31## ##STR32## 18 CN ##STR33## ##STR34## ##STR35## 19 CN ##STR36## ##STR37## ##STR38## 20 CN CO.sub.2 CH.sub.2 (CF.sub.2).sub.4 H ##STR39## ##STR40## 21 CN ##STR41## ##STR42## H 22 ##STR43## CN ##STR44## ##STR45## 23 CO.sub.2 CH.sub.2 C.sub.6 F.sub.13 CN ##STR46## Cl 24 ##STR47## ##STR48## CH.sub.3 OCOCH.sub.3 25 CN CO.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 ##STR49## ##STR50## 26 CN ##STR51## ##STR52## ##STR53## 27 CN CF.sub.3 ##STR54## Cl 28 ##STR55## CF.sub.3 ##STR56## F 29 CN ##STR57## ##STR58## ##STR59## 30 ##STR60## ##STR61## ##STR62## ##STR63## 31 CN ##STR64## ##STR65## ##STR66## 32 CN ##STR67## ##STR68## H 33 CN ##STR69## ##STR70## OSO.sub.2 CH.sub.3 ##STR71## No. R.sub.1 R.sub.2 R.sub.4 X 34 CO.sub.2 C.sub.2 H.sub.5 CN ##STR72## Cl 35 CN ##STR73## ##STR74## H 36 CN CO.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2).sub.6 F ##STR75## ##STR76## 37 CN ##STR77## ##STR78## ##STR79## 38 CN ##STR80## ##STR81## ##STR82## 39 CN ##STR83## ##STR84## H 40 CN ##STR85## ##STR86## Cl 41 CN ##STR87## ##STR88## OSO.sub.2 CH.sub.3 (42) ##STR89## (43) ##STR90## (44) ##STR91## (45) ##STR92## (46) ##STR93##
TABLE A __________________________________________________________________________ E.sub.R No. R'.sub.11 R'.sub.12 V.sub.2 V.sub.3 V.sub.6 V.sub.7 X.sub.1 R.sub.1 (V vs SCE) __________________________________________________________________________ A-1 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H H H I.sup.⊖ 1 -1.27 A-2 " " CH.sub.3 CH.sub.3 H H " " -1.29 A-3 " " CH.sub.3 H CH.sub.3 H " " -1.29 A-4 " " CH.sub.3 H H CH.sub.3 " " -1.28 A-5 " " H CH.sub.3 H CH.sub.3 " " -1.27 A-6 " " CH.sub.3 O H H H " " -1.27 A-7 " " H CH.sub.3 O H H " " -1.27 A-8 " " CH.sub.3 O CH.sub.3 O H H " " -1.29 A-9 " " CH.sub.3 O H CH.sub.3 O H " " -1.30 A-10 " " H CH.sub.3 O H CH.sub.3 O " " -1.28 A-11 " " CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 " " -1.33 A-12 " " CH.sub.3 O CH.sub.3 O CH.sub.3 O CH.sub.3 O " " -1.34 A-13 " " N(CH.sub.3).sub.2 H H H " " -1.28 A-14 (CH.sub.2).sub.3 SO.sub.3.sup.⊖ " CH.sub.3 H CH.sub.3 H -- -- -1.29 A-15 (CH.sub.2).sub.4 SO.sub.3.sup.⊖ " CH.sub.3 H CH.sub.3 H -- -- -1.29 A-16 (CH.sub.2).sub.3 SO.sub.3.sup.⊖ (CH.sub.2).sub.3 SO.sub.3.sup.⊖ CH.sub.3 H CH.sub.3 H NH.sup.⊕ (C.sub.2 H.sub.5).sub.3 1 -1.29 A-17 (CH.sub.2).sub.4 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 H I.sup.⊖ 1 -1.29 __________________________________________________________________________ (A-18.) ##STR95## (A-19.) ##STR96## (B-1) ##STR97## (B-2) ##STR98## (B-3) ##STR99## (C-1) ##STR100## (C-2) ##STR101## (C-3) ##STR102## (C-4) ##STR103## (C-5) ##STR104## (D-1) ##STR105## (D-2) ##STR106## (D-3) ##STR107## (D-4) ##STR108## The dyes represented by the general formulae (A), (B), (C) and (D) to be used in the present invention can be easily synthesized by any proper methods as disclosed in F. M. Hamer, "Heterocyclic Compounds-Cyanine Dyes and Related Compounds", Chapter IX, pp. 270-287, Chapter VII, pp. 200-243, Chapter XIV, pp. 511-611, John Wiley and Sons, 1964, D. M. Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry", Chapter VIII, sec. IV, pp. 482-515, John Wiley and Sons,
__________________________________________________________________________ Photographic constituent JP-A-62-215272 JP-A-2-33144 EP0,355,660A2 __________________________________________________________________________ Silver halide Line 6, upper right column, Line 16, upper right column, Line 53, p. 45-line 3, emulsion p. 10-line 5, lower left p. 28-line 11, lower right p 47 & line 20-line 22, column, p. 12 & last line 4, column, p. 29 & line 2- p. 47 lower right column, line 5, p. 30 p. 12-line 17, upper left column, p. 13 Silver halide Line 6-line 14, lower -- -- solvent left column, p. 12 & last line 3, upper left column, p. 13-last line, lower left column, p. 18 Chemical Last line 3, lower left Line 12-last line, Line 4-line 9, sensitizer column-last line 5, lower lower right column, p. 47 right column, p. 12 & line 1, p. 29 lower right column, p. 18-last line 9, upper right column, p. 22 Spectral Last line 8, upper right Line 1-line 13, upper Line 10-line 15, sensitizer column, p. 22-last left column, p. 30 p. 47 (spectral line on p. 38 sensitizing process) Emulsion Line 1, upper left column, Line 14, upper left Line 16-line 19, stabilizer p. 39-last line, upper column-line 1, upper p. 47 right column, p. 72 right, p. 30 Development Line 1, lower left column, -- -- accelerator p. 72-line 3, upper right column, p. 91 Color coupler Line 4, upper right column, Line 14, upper right column, Line 15-line 27, (cyan, magenta, p. 91-line 6, upper left p. 3-last line, upper p. 4, & line 30, yellow couplers) column, p. 121 left column, p. 35 p. 5-last line on p. 28, & line 29- line 31, p. 45 & line 23, p. 47- line 50, p. 63 Color Line 7, upper left column, -- -- intensifier p. 121-line 1, upper right column, p. 125 Ultraviolet Line 2, upper right column, Line 14, lower right column, Line 22-line 31, absorbent p. 125-last line, lower p. 37-line 11, upper left p. 65 left column, p. 127 column, p. 38 Discoloration Line 1, lower right column, Line 12, upper right column, Line 30, p. 4-line 23, inhibitor p. 127-line 8, lower left p. 36-line 19, upper left p. 5, & line 1, (image column, p. 137 column, p. 37 p. 29-line 25, p. 45, stabilizer) & line 33-40, p. 45 & line 2-21, p. 65 High boiling Line 9, lower left column, Line 14, lower right column, Line 1-51, p. 64 and/or low p. 137-last line, upper p. 35-last line 4, upper boiling organic right column, p. 144 left column, p. 36 solvent Process for Line 1, lower left column, Line 10, lower right column, Line 51, p. 63-line 56, dispersion p. 144-line 7, upper right p. 27-last line, upper p. 64 of photographic column, p. 146 left column, p. 28 & line 12, additives lower right column-line 7, upper right column, p. 36 Film Line 8, upper right column, -- -- hardener p. 146-line 4, lower left column, p. 155 Developing Line 5, lower left column, agent p. 155-line 2, lower right precursor column, p. 155 Development Line 3-9, lower right -- -- inhibitor- column, p. 155 releasing compound Support Line 19, lower right column, Line 18, upper right Line 29 on p. 66-line 13 p. 155-line 14, upper column, p. 38-line 3, on p. 67 left column, p. 156 upper left column, p. 39 Constitution Line 15, upper left column, Line 1-15, upper right Line 41-52, p. 45 of light- p. 156-line 14, lower column, p. 28 sensitive right column, p. 156 layers Dye Line 15, lower right column, Line 12, upper left Line 18-line 22, p. 156-last line, lower column,-line 7, upper p. 66 right column, p. 184 right column, p. 38 Diacoloration Line 1, upper left column, Line 8-11, upper right Line 57 on p. 64- inhibitor p. 185-line 3, lower column, p. 36 line 1 on p. 65 right column, p. 188 Gradation Line 4-8, lower right -- -- adjustor column, p. 188 Stain Line 9, lower right column, Last line, upper left Line 32, p. 65-line 17, inhibitor p. 188-line 10, lower column-line 13, lower p. 66 right column, p. 193 right column, p. 37 Surface Line 1, lower left column, Line 1, upper right column, -- active p. 201-last line, upper p. 18-last line, lower agent right column, p. 210 right column, p. 24 & last line 10, lower left column-line 9, lower right column, p. 27 Fluorine- Line 1, lower left column, Line 1, upper left column, -- containing p. 210-line 5, lower p. 25-line 9, lower compound left column, p. 222 right column, p. 27 (antistatic agent, coating aid, lubricant, adhesion inhibitor) Binder Line 6, lower left column, Line 8-18, upper left Line 23-28 on p. 66 (hydrophilic p. 222-last line, upper column, p. 38 colloid) left column, p. 225 Thickening Line 1, upper right column, -- -- agent p. 225-line 2, upper right column, p. 227 Antistatic Line 3, upper right column, -- -- agent p. 227-line 1, upper left column, p. 230 Polymer latex Line 2, upper left column, -- -- p. 230-last line, p. 239 Matting agent Line 1, upper left column, -- -- p. 240-last line, upper right column, p. 240 Photographic Line 7, upper right column, Line 4, upper left column, Line 14, p. 67-line processing p. 3-line 5, upper right p. 39-last line, upper 28, p. 69 method column, p. 10 left column, p. 42 (processing step, additives, etc.) __________________________________________________________________________ Note) The contents cited in JPA-62-215272 include the contents described in the written amendment of procedure dated March 16, 1987 attached thereto. Among the above mentioned color couplers, as yellow couplers there may also be preferably used short wave type yellow couplers as disclosed in JPA-63-231451, JPA-63-123047, JPA-63-241547, JPA-1-173499, JPA-1-213648, and JPA-1-250944. Further, cycloalkane acetonitride yellow couplers as described in JPA-4-116643 and indolinocarbonylanilide yellow couplers as described in EP0,482,552 may be preferably used.
______________________________________ 1st layer (blue-sensitive emulsion layer) Above mentioned silver 0.27 bromochloride emulsion B (6:4 (silver molar ratio) of a large size emulsion B.sub.1 comprising cubic grains having an average grain size of 0.88 μm and a grain size distribution fluctuation coefficient of 0.10 and a small size emulsion B.sub.2 comprising cubic grains having an average grain size of 0.70 μm and a grain size distribution fluctuation coefficient of 0.08, both comprising silver halide grains 0.3 mol % silver bromide localized partically on the grain surface, the rest being silver chloride Gelatin 1.36 Yellow coupler (ExY) 0.79 Dye image stabilizer (Cpd-1) 0.08 Dye image stabilizer (Cpd-2) 0.04 Dye image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 2nd layer (color mixing inhibiting layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 3rd layer (green-sensitive emulsion layer) Silver bromochloride emulsion G 0.13 (6:4 (Ag molar ratio) mixture of a large size emulsion G.sub.1 of cubic grains having an average size of 0.55 μm with a grain size distribution fluctuation coefficient of 0.10 and a small size emulsion G.sub.2 of cubic grains having an average size of 0.39 μm with a grain size distribution fluctuation coefficient of 0.08, 0.8 mol % of silver bromide being localized partially on the surface of each emulsion, the rest being silver halide grains) Gelatin 1.45 Magenta coupler (ExM) 0.16 Dye image stabilizer (Cpd-6) 0.15 Dye image stabilizer (Cpd-2) 0.03 Dye image stabilizer (Cpd-7) 0.01 Dye image stabilizer (Cpd-8) 0.01 Dye image stabilizer (Cpd-9) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15 4th layer (color mixing inhibiting layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Dye Image Stabilizer (Cpd-5) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 5th layer (red-sensitive emulsion layer) Above mentioned silver 0.20 bromochloride emulsion R Gelatin 0.85 Cyan coupler (Exemplary Compound 11) 0.33 Ultraviolet absorbent (UV-2) 0.18 Dye image stabilizer (Cpd-1) 0.33 Dye image stabilizer (Cpd-10) 0.15 Dye image stabilizer (Cpd-11) 0.15 Dye image stabilizer (Cpd-12) 0.01 Dye image stabilizer (Cpd-9) 0.01 Dye image stabilizer (Cpd-8) 0.01 Solvent (Solv-6) 0.22 Solvent (Solv-1) 0.01 6th layer (ultraviolet abosrbing layer) Gelatin 0.55 Ultraviolet absorbent (UV-1) 0.40 Dye image stabilizer (Cpd-13) 0.15 Dye image stabilizer (Cpd-6) 0.02 7th layer (protective layer) Gelatin 1.13 Acryl-modified copolymer of 0.15 polyvinyl alcohol (modification degree: 17%) Liquid paraffin 0.03 Dye image stabilizer (Cpd-14) 0.01 ______________________________________
TABLE B __________________________________________________________________________ Specimen No. Cyan coupler used in 5th layer Sensitizing dye used in 5th layer __________________________________________________________________________ 101 Exemplary Compound (11) A-17 102 Comparative Coupler 1 B-3 103 " Sens. 1 104 " Sens. 2 105 " Sens. 3 106 " A-17 107 Comparative Coupler 2 A-17 108 Exemplary Compound (11) B-3 109 " C-1 110 " D-1 111 " Sens. 1 112 " Sens. 2 113 " Sens. 3 114 Exemplary Compound (10) A-17 115 Exemplary Compound (12) A-17 116 Exemplary Compound (14) " 117 Exemplary Compound (16) " 118 Exemplary Compound (18) " 119 Exemplary Compound (20) " 120 Exemplary Compound (21) " 121 Exemplary Compound (34) " (Sens-1) ##STR120## (Sens-2) ##STR121## (Sens-3) ##STR122## Comparative Coupler 1 ##STR123## Comparative Coupler 2 ##STR124## __________________________________________________________________________
______________________________________ Processing Tank step Temperature Time Replenisher* capacity ______________________________________ Color 35° C. 45 sec. 161 ml 17 l development Blix 30-35° C. 45 sec. 215 ml 17 l Rinse 30° C. 90 sec. 350 ml 10 l Drying 70-80° C. 60 sec. ______________________________________ *The replenishment rate is represented per m.sup.2 of lightsensitive material.
______________________________________ Running Color developer Solution Replenisher ______________________________________ Water 800 ml 800 ml Ethylenediamine-N,N,N',N'- 1.5 g 2.0 g tetramethylenephosphonic acid Potassium bromide 0.015 g -- Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g -- Potassium carbonate 25 g 25 g N-ethyl-N-(β-methanesulfon- 5.0 g 7.0 g amidoethyl)-3-methyl-4- aminoanilinesulfate N,N-bis(carboxymethyl)- 4.0 g 5.0 g hydrazine N,N-di(sulfoethyl)hydroxyl- 4.0 g 5.0 g amine.1Na Fluorescent brigthening agent 1.0 g 2.0 g (WHITEX 4B, available from Sumitomo Chemical Co., Ltd.) Water to make 1,000 ml 1,000 ml pH (25° C.) 10.05 10.45 ______________________________________ Blix solution (running solution was used also as replenisher) Water 400 ml Ammonium thiosulfate (700 g/l) 100 ml Sodium sulfite 17 g Ammonium ethylenediaminetetraacetate 55 g (III) Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water to make 1,000 ml pH (25° C.) 6.0 ______________________________________
TABLE C ______________________________________ Ageing of coating Dependence on solution (sensitivity at exposure temperature coating 4 hr. ageing- Specimen (sensitivty at 35° C.- sensitivity at coat- No. sensitivity at 15° C.) ing 30 min. ageing) ______________________________________ 101 ±0 -0.01 102 0.03 -0.06 103 0.06 -0.03 104 0.06 -0.04 105 0.07 -0.03 106 0.03 -0.07 107 0.03 -0.07 108 0.02 -0.01 109 0.02 -0.02 110 0.02 -0.01 111 0.06 -0.03 112 0.06 -0.02 113 0.05 -0.03 114 ±0 ±0 115 ±0 -0.01 116 " ±0 117 " -0.01 118 " -0.01 119 " -0.01 120 " -0.01 121 " -0.01 ______________________________________ (Note: Specimens 101, 108 to 110, and 114 to 121 are according to the present invention)
TABLE D ______________________________________ Sensitizing Emulsion Specimen Cyan coupler used dye used in used in No. in 5th layer 5th layer 5th layer ______________________________________ 101 Exemplary Compound (11) A-17 R.sub.1, R.sub.2 103 Comparative Coupler 1 Sens. 1 " 107 Comparative Coupler 2 A-17 " 108 Exemplary Compound (11) B-3 " 109 " C-1 " 110 " D-1 " 111 " Sens. 1 " 201 Exemplary Compound (11) A-17 R.sub.3, R.sub.4 203 Comparative Coupler 1 Sens. 1 " 207 Comparative Coupler 2 A-17 " 208 Exemplary Compound (11) B-3 " 209 " C-1 " 210 " D-1 " 211 " Sens. 1 " ______________________________________
TABLE E ______________________________________ Ageing of coating Dependence on solution (sensitivity at exposure temperature coating 4 hr. ageing- Specimen (sensitivty at 35° C.- sensitivity at coat- No. sensitivity at 15° C.) ing 30 min. ageing) ______________________________________ 101 ±0 ±0 103 0.06 -0.03 107 0.03 -0.07 108 0.02 -0.02 109 0.02 -0.02 110 0.02 -0.02 111 0.06 -0.03 201 ±0 ±0 203 0.05 -0.03 207 0.03 -0.06 208 0.02 -0.02 209 0.02 -0.02 210 0.02 -0.02 211 0.06 -0.03 ______________________________________ (Note: Specimens 101, 108 to 110, 201, and 208 to 210 are according to th present invention)
__________________________________________________________________________ 1st layer (blue-sensitive emulsion layer) Silver bromochloride emulsion B of Example 1 0.30 Gelatin 1.22 Yellow coupler (Ex5Y) 1.01 Dye image stabilizer (Cpd-17) 0.19 Solvent (Solv-8) 0.18 Solvent (Solv-1) 0.18 Dye image stabilizer (Cpd-1) 0.06 2nd layer (color mixing inhibiting layer) Gelatin 0.64 Color mixing inhibitor (Cpd-4) 0.10 Solvent (Solv-2) 0.16 Solvent (Solv-3) 0.08 3rd layer (green-sensitive emulsion layer) Silver bromochloride emulsion G of Example 1 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Dye image stabilizer (Cpd-9) 0.03 Dye image stabilizer (Cpd-6) 0.16 Dye image stabilizer (Cpd-18) 0.02 Dye image stabilizer (Cpd-2) 0.02 Solvent (Solv-7) 0.40 4th layer (ultraviolet abosrbing layer) Gelatin 1.41 Ultraviolet absorbent (UV-3) 0.47 Color stain inhibitor (Cpd-4) 0.05 Solvent (Solv-8) 0.24 5th layer (red-sensitive emulsion layer) Silver bromochloride emulsion R of Example 1 0.23 Gelatin 1.04 Cyan coupler (Exemplary Compound 11) 0.32 Dye image stabilizer (Cpd-9) 0.03 Dye image stabilizer (Cpd-18) 0.02 Ultraviolet absorbent (UV-2) 0.18 Dye image stabilizer (Cpd-1) 0.40 Dye image stabilizer (Cpd-19) 0.05 Solvent (Solv-10) 0.14 6th layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbent (UV-3) 0.16 Color stain inhibitor (Cpd-4) 0.02 Solvent (Solv-9) 0.08 7th layer (protective layer) Gelatin 1.10 Acryl-modified copolymer of polyvinyl alcohol (modification degree: 0.17 Liquid paraffin 0.03 __________________________________________________________________________ Dye image stabilizer (Cpd-17) ##STR126## Dye image stabilizer (Cpd-18) ##STR127## __________________________________________________________________________
TABLE F __________________________________________________________________________ Specimen No. Cyan coupler used in 5th layer Sensitizing dye used in 5th layer __________________________________________________________________________ 101 Exemplary Compound (11) A-17 501 Comparative Coupler 3 " 502 Comparative Coupler 4 " 503 Comparative Coupler 5 " 504 Comparative Coupler 6 " 505 Comparative Coupler 7 " 506 Comparative Coupler 8 " 507 Comparative Coupler 9 " 508 Exemplary Compound (11) A-2 509 " A-4 510 " A-6 511 " A-8 512 " A-10 513 " A-12 514 " A-14 515 " A-16 516 " A-18 517 " B-1 518 " B-2 519 " C-3 520 " C-4 521 " D-3 522 " D-4 523 " Sens. 4 524 " Sens. 5 525 " Sens. 6 526 " Sens. 7 527 " Sens. 8 528 " Sens. 9 529 " Sens. 10 530 Exemplary Compound (2) A-10 531 Exemplary Compound (4) " 532 " " 533 Exemplary Compound (6) " 534 Exemplary Compound (22) " 535 Exemplary Compound (25) " 536 Exemplary Compound (29) " 537 Exemplary Compound (31) " 538 Exemplary Compound (33) " 539 Exemplary Compound (35) " 540 Exemplary Compound (38) " __________________________________________________________________________ <Comparative spectral sensitizing dye> Sens. 4 ##STR132## Sens. 5 ##STR133## Sens. 6 ##STR134## Sens. 7 ##STR135## Sens. 8 ##STR136## Sens. 9 ##STR137## Sens. 10 ##STR138## Comparative coupler 3 ##STR139## Comparative coupler 4 ##STR140## Comparative coupler 5 ##STR141## Comparative coupler 6 ##STR142## Comparative coupler 7 ##STR143## Comparative coupler 8 ##STR144## Comparative coupler 9 ##STR145##
TABLE G ______________________________________ Ageing of coating Dependence on solution (sensitivity at exposure temperature coating 4 hr. ageing- Specimen (sensitivty at 35° C.- sensitivity at coat- No. sensitivity at 15° C.) ing 30 min. ageing) ______________________________________ 101 ±0 -0.02 501 0.02 -0.06 502 0.02 -0.06 503 0.02 -0.07 504 0.03 -0.05 505 0.02 -0.06 506 0.02 -0.06 507 0.02 -0.07 508 ±0 -0.01 509 ±0 -0.01 510 ±0 -0.01 511 ±0 -0.01 512 ±0 -0.01 513 ±0 -0.01 514 ±0 -0.01 515 ±0 -0.01 516 ±0 -0.01 517 0.02 -0.02 518 0.02 -0.02 519 0.02 -0.02 520 0.02 -0.02 521 0.02 -0.01 522 0.02 -0.02 523 0.06 -0.02 524 0.05 -0.02 525 0.06 -0.02 526 0.05 -0.01 527 0.06 -0.02 528 0.06 -0.02 529 0.06 -0.02 530 ±0 -0.01 531 ±0 -0.01 532 ±0 -0.01 533 ±0 -0.01 534 ±0 -0.01 535 ±0 -0.01 536 ±0 -0.01 537 ±0 -0.01 538 ±0 -0.01 539 ±0 -0.01 540 ±0 -0.01 ______________________________________ (Note: Specimens 101, 508 to 522, and 530 to 540 are according to the present invention)
Claims (26)
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JP4-165481 | 1992-06-02 | ||
JP4165481A JP2890224B2 (en) | 1992-06-02 | 1992-06-02 | Silver halide color photographic materials |
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US20050008982A1 (en) * | 2003-05-12 | 2005-01-13 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material and image forming method |
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JPH07140612A (en) * | 1993-11-16 | 1995-06-02 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
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EP0313021A1 (en) * | 1987-10-19 | 1989-04-26 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US4950585A (en) * | 1987-08-18 | 1990-08-21 | Konica Corporation | Coupler for photographic use |
US5057402A (en) * | 1988-01-18 | 1991-10-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US5091297A (en) * | 1988-05-17 | 1992-02-25 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
EP0488248A1 (en) * | 1990-11-28 | 1992-06-03 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
US5164289A (en) * | 1990-05-11 | 1992-11-17 | Fuji Photo Film Co., Ltd. | Dye forming coupler and silver halide color photographic material containing the same and method for forming color image |
US5176993A (en) * | 1989-10-06 | 1993-01-05 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US5206130A (en) * | 1990-11-06 | 1993-04-27 | Fuji Photo Film Co., Ltd. | Cyan coupler, cyan image forming method using the same and silver halide color photographic material containing the same |
US5215871A (en) * | 1990-11-07 | 1993-06-01 | Fuji Photo Film Co., Ltd. | Method of forming cyan image with cyan dye forming coupler, and silver halide color photographic material containing the cyan dye forming coupler |
US5256526A (en) * | 1990-11-30 | 1993-10-26 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
-
1992
- 1992-06-02 JP JP4165481A patent/JP2890224B2/en not_active Expired - Fee Related
-
1993
- 1993-06-02 US US08/070,294 patent/US5462847A/en not_active Expired - Lifetime
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US4950585A (en) * | 1987-08-18 | 1990-08-21 | Konica Corporation | Coupler for photographic use |
EP0313021A1 (en) * | 1987-10-19 | 1989-04-26 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US5057402A (en) * | 1988-01-18 | 1991-10-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US5091297A (en) * | 1988-05-17 | 1992-02-25 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US5176993A (en) * | 1989-10-06 | 1993-01-05 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US5164289A (en) * | 1990-05-11 | 1992-11-17 | Fuji Photo Film Co., Ltd. | Dye forming coupler and silver halide color photographic material containing the same and method for forming color image |
US5206130A (en) * | 1990-11-06 | 1993-04-27 | Fuji Photo Film Co., Ltd. | Cyan coupler, cyan image forming method using the same and silver halide color photographic material containing the same |
US5215871A (en) * | 1990-11-07 | 1993-06-01 | Fuji Photo Film Co., Ltd. | Method of forming cyan image with cyan dye forming coupler, and silver halide color photographic material containing the cyan dye forming coupler |
EP0488248A1 (en) * | 1990-11-28 | 1992-06-03 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
US5270153A (en) * | 1990-11-28 | 1993-12-14 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
US5256526A (en) * | 1990-11-30 | 1993-10-26 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20050008982A1 (en) * | 2003-05-12 | 2005-01-13 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material and image forming method |
US7153644B2 (en) * | 2003-05-12 | 2006-12-26 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material and image forming method |
Also Published As
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JP2890224B2 (en) | 1999-05-10 |
JPH05333500A (en) | 1993-12-17 |
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